Treatment of textiles with alkylamidoalkene orthosilicates



Patented Aug. 2, 1949 TREATMENT OF TEXTILES WITH ALKYL- 1- ALIIDOALKENEORTHOSILICATES Ernst Zerner and Marcel Gradsztain, New York, N. Y.,assignors, by mesne assignments, to Sun Chemical Corporation, New York,N. Y., a corporation of Delaware No Drawing. Application September 24.1945, Serial No. 618,392

2Claims. (Cl. 117-121) This invention relates to a novel process fortreating textile materials, including in this term fabrics and threadsof natural material, as cotton, jute, linen, hemp, wool, and artificialmaterial, as viscose, acetate, etc.

More particularly, this invention relates to th process of waterproofingsuch materials.

It is an object of this invention to make the materials treated not onlywater repellent, but also to produce a water repellent effect fast tocommercial cleaning methods, particularly the usual dry cleaning.

Other objects will appear hereinafter.

These objects are accomplished according to our invention by treatingthe textile materials with an organic silicon compound containing atleast one long chain fatty radical.

Such compounds may be esters of silicic acid formed with alcoholscontaining a long chain fatty radical. In this case the bond of the longchain fatty radical with the Si-atom is performed by oxygen, as forinstance in tetrahexadecylsilicate (C1cHa30)4Si.

Some representatives of this type of compounds are already described inthe literature, and known methods can be used to prepare other productsof the same type.

Silicic acid esters, for instance, which can be used according to ourinvention, are easily produced in verygood yields by reacting $1014 withalcohols containing a long chain fatty radical, generally in thepresence of an indiflerent solvent. We have found that the radical mustcontain a chain of at least 12 carbon atoms inorder to effect thedesired water repellency.

Alcohols suitable for our purposes are, for instance, lauryl alcohol andits higher homologues like myristyl alcohol, cetyl alcohol, stearylalcohol,

or montanyl alcohol. Secondary alcohols of suilicient chain length asmentioned above are also suitable, as for instance, tetradecanol orheptadecanol. Hydroxylated aromatic compounds likeortho-octadecyloxyphenol are also suitable. Long chain fatty acidamides, in which the amide group is linked with a hydroxylatedgroup likeethanolstearamide CuHssCONHCHaCHzOH or oxymethylstearamideCnHssCONHCHaOH are also suitable for our purposes.

The above mentioned hydrox'ylated compounds 2 may first be convertedinto the corresponding halogenldes, submitted to reaction with Mg andfinally, after formation of the Grignard compound, reacted with SiClc'Textiles are treated with the above mentioned compounds by padding themin a solution of these compounds in suitable organic solvents likebenzene, kerosene, Stoddard solvent, etc., in a comparatively lowconcentration of about 0.5-5 squeezing out the excess of solution anddrying at elevated temperatures of 70-160 for a period of severalminutes to some hours.

Instead of using solutions of the compounds mentioned before in organicsolvents, they may also be emulsified and aqueous emulsions applied totextiles in a similar way as described above.

We discovered that it is essential to perform the drying at elevatedtemperatures. If higher temperatures are used, the time of drying may beconsiderably shortened. Time and temperature vary individually accordingto the various silicon compounds.

It is amazing that a compound applied to a 'cloth in a Stoddard solutionshould not be removed by subsequent dry cleaning by the same solvent, i.e., Stoddard solution. It is our belief that the original monomersilicon compound polymerizes on the cloth during the heating instance,on cotton. In the case of' the usual so-called permanent waterrepellents, mostly quaternary ammonium compounds, it is observed thatthe effect on acetate is far inferior to that on non-esterlfiedcellulose. This is explained by the fact that a reaction occurs with thecellulose, very probably an etherification of the free hydroxyl groups,which cannotbe effected at all, or only to a much smaller extent, onacetate, where at least a part of the hydroxyl groups is alreadysubstituted.

In order to promote the polymerization of our silicon compounds, 2. verysmall amount of HCl may be added to the padding solution, and the sameallowed to stand for a prolonged period. In using this procedure wenoticed a substantial improvement in some cases 'where the originalspray rating and fastness to dry cleaning were not quite satisfactory.

The following examples are given to illustrate 3 more in detail thepreparation of our material and its application to textiles; without,however, limiting our invention to a particular procedure.

- Example I 104 g. stearyl alcohol were dissolved in 300 ml. drybenzene. The solution was slowly added to 17 g. silicon tetrachloridewith stirring. Hydrochloric acid gas was evolved. When the reactionslowed down. the temperature was gradually raised and the mixturerefluxed on the boiling water bath for.2.5 hours. At the end of theheating period dry nitrogen was passed through the reaction product todrive out the remaining hydrochloric acid. After elimination of thebenzene by distillation a white waxy mass was obtained.

The reaction product corresponds in all probability to the formula(CmHmO) 481. (Si calculated 2.54%, found 2.40%.)

A piece of gabardine was dipped in a 2.5% solution of the above productin Stoddard solvent, the excess of solution squeezed out by a roller andthe fabric then kept for 30 minutes at 120 C. The repellency was testedfollowing the procedure of the 1944 Year Book of the AmericanAssociation of Textile Chemists and Colorists (pp. 200-211). The initialspray rating was 100 and went down to about 80 after three successivedry cleanings.

Example II To a mixture of 355 g. commercial stearamide, 40 g.paraformaldehyde and 1000 ml. dry benzene, g. silicon tetrachloride wereadded. The mixture was heated up to 50 C. with vigorous stirringand-after a few minutes the mass thickened, indicating the formation ofoxymethylstearamide. The mixture was allowed to cool down to 30 C. Tothe resulting viscous mass 50 g. silicon-tetrachloride diluted with asubstantially equal volume of dry benzene were added,

and the temperature gradually raised to 70 C. This temperature wassustained for three hours under continuous stirring. Hydrochloric acidgas was evolved in considerable quantity. At the end of the heatingperiod, dry nitrogen was blown through the reaction mass and eventuallythe solvent distilled off under reduced pressure. The residue of thedistillation was a brown, brittle mass which did not dissolve completelyin stmdard solvent. After elimination of the little insoluble part byfiltration, the filtrate was brought to a concentration of 3% and usedfor padding.

The assumed formula of the product is (CnHssCONHCHzO) 431 (Si found2.43%, calculated 2.2%.)

Plain weave gray cotton cloth was treated as described in Example I,with the only difference that the padded fabric was heated for threeminutes only, to 150 C. Initial spray rating 100;

after three consecutive dry cleanings 90.

Similar results as to water repellency were obtained on gabardine and ona fabric consisting of 6 50% acetate and 50% viscose.

Example III the Gria'nard solution was added to 11.5 g. silicontetrachloride dissolved in 50 ml. dry ether under vigorous stirring.After this addition the reaction mass was refluxed on the water bath for5 70 minutes. Then the reaction product was decomposed with a. fewpieces of ice. Decomposition had to be done very cautiously and with aslittle ice as possible, to avoid formation of emulsions and consequentlyloss or material. The ethereal layer was washed with water toneutrality, dried with anhydrous sodium sulphate, and the etherdistilled oil. The residue was a yellowish waxy mass. Yield about 20 8.

Loose wool was padded with a 2.5% Stoddard solution of this material,excess of solvent I squeezed out and the wool then heated for 5 minutesto 140 C. Original spray rating 90; after three dry cleanings, 70.

In another padding a few bubbles of dry hydrochloric acid wereintroduced in the 2.5 Stoddard solutiom of the material. Thehydrochloric acid content determined by titration was 0.2 mg. per 1 ml.solution. This solution was allowed to stand over night and loose woolwas padded in it the fojllowing day and further treated as described aove. 1

Initial spray rating, 100; hardly affected by three successive drycleanings.

The above description and examples do not limit the scope of thisinvention in any way, since numerous modifications may be made withoutmaterial departure from the salient features of the invention asexpressed in the appended claims.

What we claim is:

1. The process of improving textile materials whereby to impart theretowater repellent properties fast to commercial cleaning methods, whichcomprises treating the raw materials with a solution of analkylamido-alkene orthosilicate, in which the alkyl group contains atleast 12 and not more than 30 carbon atoms, and thereafter heating saidtreated material at a temperature within the range of approximately70-160 C.

2. The process of improving textile material which comprises the stepsof treating said textile material with a composition includingstearamidomethylene orthosilicate, and thereafter heating said treatedmaterial at a temperature within the range of approximately 70-160 0.,whereby said improved textile material exhibits water repellent.properties fast to commercial cleaning methods.

ERNST ZERNER. MARCEL GRADSZTAIN.

REFERENCES CITED The following referenices are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,053,474 Graves Sept. 8, 19362,118,898 Price May 31, 1938 2,306,222 Patnode Dec. 22, 1942 2,386,259Norton Oct. 9, 1945 2,390,370 Hyde Dec. 4, 1945 OTHER REFERENCESScientific American, Jan. 1945, p. 28.

Rochow; Chemistry of the Silicones, John Wiley & Sons, Inc., N. Y.,1946; pp. 61 and 122.

